Romp with oligomeric UV-absorbers

ABSTRACT

The invention relates to metathesis polymers wherein an aromatic group that has UV-light absorbing properties is attached with a bridge group to the polymer. Also disclosed is a polymerizable composition comprising a catalytically effective amount of a penta- or hexavalent ruthenium or osmium carbene catalyst, the process for preparing the metathesis polymer by applying the reaction conditions of Ring Opening Metathesis Polymerization (=ROMP) to the polymerizable composition; and various technical applications of the metathesis polymers.

The invention relates to compounds wherein one or more groups havingUV-light absorbing properties are attached with bridge groups to anoligomer moiety, to the use of these compounds as stabilisers againstdegradation by light, heat or oxidation, particularly as stabilisers ofsynthetic polymers.

The invention particularly relates to metathesis oligomers wherein anaromatic group that has UV-light absorbing properties is attached with abridge group to the oligomer; a polymerisable composition comprising acatalytically effective amount of a penta- or hexavalent ruthenium orosmium carbene catalyst, the process for preparing the metathesispolymer by applying the reaction conditions of Ring Opening MetathesisPolymerisation (=ROMP) to the polymerisable composition; and varioustechnical applications of the metathesis polymers.

Thermal ROMP of cycloolefins other than cyclohexene has acquired greatimportance. This method requires appropriate catalysts. Catalysts ofparticular interest for ROMP are so-called metal carbenes, for exampleruthenium and osmium complexes, bearing the group ═CR′R″ (wherein one ofR′ and R″ represents hydrogen and the other represents phenyl, alkyl oralkenyl or both represent alkyl or alkenyl) attached to the centralmetal atom [WO 93/20111; S.Kanaoka et al., Macromolecules 28:4707-4713(1995); C.Fraser et al., Polym. Prepr. 36:237-238 (1995); P. Schwab etal., Angew. Chem. 107:2179-2181 (1995)]. WO 99/00396 disclosescompositions of pentavalent and hexavalent ruthenium and osmium carbenecomplex catalysts in admixture with dicyclopentadiene or cycloolefinsother than cyclohexene.

UV-absorbers are substances which absorb radiant energy in thewavelength of UV. Suitable UV-absorbers are2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters ofsubstituted or unsubstituted benzoic acids or2-(2-hydroxyphenyl)-1,3,5-triazines. Added to polymers they filter offthe UV-components of the electromagnetic irradiation and decrease lightsensitivity and consequent discoloration and degradation.

A particular useful application of UV-absorbers in polymers is their usein so-called greenhouse films. Some types of crops are degraded by theUV-components of solar radiation which must be filtered off to obtainhigh quality and productivity of the crops. Additionally, somemicro-organisms, e.g. Botrytis Cinerea, can proliferate under specificUV-irradiation. These pest are harmful for the cultivation of somevarieties of roses [R. Reuven et al., Development of photoselective PEfilms for control of foliar pathogens in greenhouse-grown crops,Plasticulture No. 102, pg. 7 (1994); Y. Eheshel et al., The use of UVabsorbing plastic sheets to protect crops against insects and spread ofvirus diseases, CIPA Congress 1997].

Another useful application of UV-absorbers in polymers is their use forrigid and flexible packaging. Some packaged goods are sensitive toUV-radiation that may induce deterioration of their characteristics. Theaddition of UV-absorbers to the polymer foil can prevent the decomposingeffect of UV-radiation on the polymer. As an example, some fresh food(meat, cheese) is subjected to fast modifications of its organolepticproperties, e.g. colour, in the event that UV-radiation is not filteredoff [M. Lennersten, Light induced Lipid Oxidation and Color Changes inFoods, Ph.D. Thesis, Department of Food Science, Chalmers Institute ofTechnology (1998)].

Therefore, it is desirable to protect the polymerisates, particularlycoatings, against the action of light by reducing the intensity ofultraviolet radiation in polymerisates exposed to visible light. It hassurprisingly been found out that the efficiency of UV-absorbers added tooligomers obtained by ROMP is greatly enhanced in the event that theUV-absorber molecules are directly linked to the oligomer structure bychemical bonds such as ether or ester bonds.

Therefore the present invention relates to a compound of the formula:A—{[B_(p)—(X—Y)_(q)][B′_(p′)—(X′—Y′)_(q′)]Z}_(r)   (I),wherein

-   -   a) one of q and q′ represents zero, one or a numeral greater        than one and the other one represents one or a numeral greater        than one;        -   A and Z represent chain terminal groups from the chain            transfer agent A(—Z)_(r);

r represents a numeral from one to four;

-   -   -   B and B′ independently of one another represent unsaturated            or hydrogenated repeating units from cycloolefins            polymerised by metathesis;        -   X and X′ represent identical or different bivalent groups;        -   Y and Y′ represent identical or different UV-light absorber            moieties; and        -   one of p and p′ represents zero, one or a numeral greater            than one and the other one represents one or a numeral            greater than one; or wherein

    -   b) q and q′ represent zero;        -   A and Z represent chain terminal groups from the chain            transfer agent A(—Z)_(r), wherein            -   A represents the chain terminal group Y″—X″—, wherein            -   Y″ represents a UV-light absorber moiety; and            -   X″ represents a bivalent group; and        -   B, B′, p, p′ and r are as defined above.

The terms and definitions used in the description of the presentinvention preferably have the following meanings:

The formula I comprises any polymeric compound wherein the lowest totalnumber of repeating units B and B′ is two. The formula I comprisespolymeric compounds of low molecular weight, such as oligomers orcooligomers, or homopolymers and copolymers of higher molecular weight,for example block, multi-block or gradient copolymers as well ascopolymers characterised by a random, hyper-branched, star-shaped ordendritic arrangement of the polymer units as well as graft copolymers.

According to the embodiment a) one of q and q′ represents zero, one or anumeral greater than one and the other one represents one or a numeralgreater than one. At least one UV-light absorber moiety —Y or —Y′ isattached with the bivalent bridge group —X— or —X′— to one or bothgroups B and B′. An additional UV-light absorber moiety may be presentin one of the chain terminal groups —A and —Z.

The indices q and q′ define the number of groups —X—Y and —X′—Y′attached to the monomer units B and B′. The fragments —X— and —X′— inthe groups —X—Y and —X′—Y′ are identical or different. Y and Y′represent identical or different UV-light absorber moieties. In theevent that one of q and q′ represents zero, at least one group —X—Y or—X′—Y′ is attached to one of the monomer units B or B′. In the eventthat one of q and q′ represents one, at least one additional group —X—Yor —X′—Y′ is attached to the monomer units B or B′. Both indices q andq′ may also represent numerals greater than one. In that event identicalor different groups —X—Y and —X′—Y′ are attached to the monomer units Band B′.

According to the embodiment b) both q and q′ represents zero. In thatevent there are no groups —X—Y or —X′—Y′ attached to the monomer units Band B′. One of A and Z then represents a chain terminal group Y″—X″—,wherein the UV-light absorber moiety Y″ is present and wherein —X″—represents a bivalent group.

The compounds (I) are obtainable by metathesis polymerisation, asopposed to other methods of polymerisation, such as ionic or freeradical polymerisation. Metathesis polymerisation is characterised bythe ring-opening polymerisation of cycloalkenes initiated by olefinmetathesis catalysts, cf. Concise Encyclopedia of Polymer Science andEngineering, J. I. Kroschwitz (editor), J. Wiley & Sons USA, 1990Edition, ISBN 0-471-51253-2, pg. 611. Representative cycloalkenespolymerisable by this method include dicyclopentadiene, norbornadiene,norbornene, cyclooctene and cyclooctadiene.

According to both embodiments a) and b) the polymerisation by metathesisis performed in the presence of the of chain transfer agents (CTA) ofthe formula A(—Z)_(r) wherein A and Z represent chain terminal groupsand r represents a numeral from one to four. Chain transfer agents areused to regulate and limit the molecular weight in a polymer reaction,cf. F. W. Billmeyer, Polymer Science, ISBN 0-471-03196-8, pg. 63.

According to the embodiment a) suitable chain transfer agents are openchain alkenes (r=1), e.g. n-butene, n-hexene or n-octene, which arepresent in the compound (I) as identical or different terminal alkylgroups A and Z. In a particularly preferred embodiment A and Z aredifferent. One of A and Z represents methyl and the other one representslinear C₃-C₇alkyl, e.g. n-propyl, n-pentyl or n-heptyl.

An alternative chain transfer agent may have a branched structurewherein two (r=2), three (r=3) or four (r=4) alkene groups are presentin separate branches. These chain transfer agents are present in thecompound (I) as bi-, tri- or tetrafunctional terminal groups A and two,three or four terminal alkyl groups Z. One additional UV-light absorbermoiety may be present in one of the chain terminal groups —A and —Z.

According to the embodiment b) no groups —X—Y or —X′—Y′ are attached tothe monomer units B and B′. In that event the UV-light absorber moietyis present in one of the chain terminal groups —A and —Z. According to apreferred embodiment the chain transfer agent has a branched structurewherein three (r=3) alkene groups are present in separate branches ofthe UV-light absorber moiety. This chain transfer agent is present inthe compound (I) as trifunctional group A wherein A is a UV-lightabsorber moiety. Z then represents methyl or linear C₃-C₇alkyl (starshaped polymers).

In a compound (I) the indices p and p′ define the number of monomerrepeating units B and B′ present in the compound (I) according to theembodiments a) and b) of the invention. One of p and p′ represents zero,one or a numeral greater than one and the other one represents one or anumeral greater than one.

In the event that one of the indices p and p′ represents zero, the otherone of p and p′ represent one or a numeral greater than one. In theevent that one of the indices p and p′ represents one, the lowest valueof p and p′ is two, which defines an oligomer wherein the number ofrepeating units B and B′ is two and wherein B and B′ are identical ordifferent. According to another embodiment of the invention one of theindices p and p′ represents one and the other one of p and p′ representsa numeral greater than one. In this case the lowest value of p and p′ isthree, which defines an oligomer wherein the number of repeating units Band B′ is three. B and B′ can be identical or different and define homo-and copolymers.

According to a preferred embodiment of the invention, p and p′ togetherrepresent numerals from 2 to 1000. The preferred molecular weight rangeis from about 600 to 100 000, particularly from about 800 to 50 000. Ahighly preferred range is from about 1000 to 5000.

A preferred embodiment of the invention relates to compound (I), whereinp and p′ together represent a numeral from 2 to 20.

The term cycloolefin polymerised or polymerisable by metathesis includesmonocyclic cycloolefins other than cyclohexene and polycyclic,polycyclic condensed (fused) or bridged or polycyclic condensed (fused)and bridged cycloolefins. The individual rings in these cycloolefinsconsist of 3 to 16, especially 3 to 12, and preferably 3 to 8 ringmembers and may contain heteroatoms selected from the group consistingof O, S, N and Si and additional substituents selected from the groupconsisting of C₁-C₄alkyl, e. g. methyl or ethyl, C₁-C₄alkoxy, e. g.methoxy or ethoxy, halogen, e.g. chloro or bromo, cyano andtrifluoromethyl.

A preferred group includes cycloolefins polymerised by metathesisselected from the group consisting of cyclopropene, cyclobutene,cyclopentene, cycloheptene, cyclooctene, cyclopentadiene,dicyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene,norbornadiene, norbornene and norbornene derivatives.

A particularly preferred group of cycloolefins includes monocycliccycloolefins having one double bond such as cyclobutene or cycloocteneand bicyclic cycloolefins having two double bonds such as1,5-cyclooctadiene.

Another preferred group of cycloolefins includes bi-, tri-, tetra- andpentacyclic bridged cycloolefins obtainable by a Diels-Alder typeaddition reaction of dienes with so-called dienophiles. The individualrings in these bridged cycloolefinic adducts may be condensed withmonocyclic or bicyclic carbocyclic aromatic groups, such as benzene ornaphthalene, or with monocyclic or bicyclic heterocyclic aromatic groupssuch as thiophene, furane, pyridine or quinoline.

This preferred group of cycloolefins includes carbocyclic bi-, tri-,tetra- and pentacyclic bridged cycloolefins obtainable by a Diels-Aldertype addition reaction, especially cycloolefins by Diels-Alder reactionof cyclopentadiene with suitable dienophiles.

A highly preferred group of cycloolefins of this type includes monomersbased on norbornene and norbornadiene selected from the group consistingofnorbornene-2,5-methoxycarbonyl-norbornene-2,5-methyl-5-methoxycarbonyl-norbornene-2,5-cyanonorbornene-2,5-methyl-5-cyanonorbornene,5,5-dicyano-norbornene-2,1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octa-hydronapthaline,6-methyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-methyl-6-methoxycarbonyl-1,4,5,8-dimethano1,4,4a,5,6,7,8,8a-octahydronapthaline,6-methoxycarbonyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-cyano-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8aoctahydronapthaline,6-ethyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-ethylidene-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6,7-dimethyl1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,1,4-dimethano-1,4,4a,9atetrahydrofluorene dicyclopentadiene,tricyclopentadiene, tetracyclopentadiene, tetracyclododecene and methyltetracyclododecene.

Cycloolefins to which a UV-light absorber molecules moiety is attachedare known or, if they are novel, are prepared in manner which is initself known, e. g. by etherifying one hydroxy group of the UV-lightabsorber molecule with an open chain alkene or a reactive derivativethereof, e.g. allyl chloride or bromide, or by esterifying analkenecarboxylic acid with the hydroxy group, thus generating adienophile which is then reacted with a diene compound in a conventionalDiels-Alder reaction.

The bivalent groups X, X′ and X′″ are bivalent atoms or groups selectedfrom the group consisting of —O—, —S—, —NH—, —N(C₁-C₄alkyl)₂-,—NH(C₁-C₄alkyl)₂-, —C(═O)—O—, —O—(O═)C—, —NH—(O═)C—, —C(═O)—NH—,—N(C₁-C₄alkyl)-(O═)C—, —C(═O)—N(C₁-C₄alkyl)-, —O—C(═O)—O—, —NH—C(═O)—O—,—O—C(═O)—NH—, —O—C(═O)—N(C₁-C₄alkyl)-, —O(C₁-C₈alkylene)- andC₁-C₈alkylene.

In a preferred embodiment of the invention X, X′ and X″ independently ofone another represent bivalent groups selected from the group consistingof —O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene.

Suitable bivalent groups X, X′ and X′″ may also consist of two of thegroups of above connected with ethylene or straight chain or branchedC₃-C₁₀-alkylene radicals, such as —O—C₂H₄—O—, —NH—C₂H₄—NH—,—NCH₃—C₂H₄—NCH₃— or any other chelate forming bivalent group known incomplex chemistry.

The bivalent groups X, X′ and X′″ are attached to each monomer unit Band B′ or, in the alternative, are attached only to some monomer unitspresent in the polymer chain.

The term UV-light absorber moiety comprises any structural moietyeffective as photostable UV-filter which is derived from UV-lightabsorber compounds present in cosmetic and pharmaceutical preparationsfor protecting the human epidermis or human hair from UV-radiation,particularly in the range from 290 to 400 nm. Examples of suitableUV-light absorber moieties are described in U.S. Pat. No. 6,132,703. Apreferred UV-light absorber moiety is a substituent selected from thegroup consisting of 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, benzoic acid esters, oxanilides and2-(2-hydroxyphenyl)-1,3,5-triazines.

Specific 2-(2′-hydroxyphenyl)benzotriazoles are2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(2′,4′-dihydroxyphenyl)-benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5-(1-hydroxycarbonyl-2-ethyl)-phenyl]-benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5-(1-hydroxycarbonyl-2-ethyl)-phenyl]-5-chlorobenzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)-phenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxy-carbonylethyl)-2′-hydroxyphenyl]-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂₂; wherein Rrepresents 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl-phenyl;2-[2′-hydroxy-3′-(α,α-di-methylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazoleand2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

Specific 2-hydroxybenzophenones are, for example, the 4-hydroxy,4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,2,4-dihydroxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxyderivatives.

Specific benzoic acid esters are, for example, 4-tert-butyl-phenylsalicylate, phenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate,2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

Specific oxanilides are, for example, 2-ethyl-2′-hydroxyoxanilide,4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butyloxanilide,2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of o- andp-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.

Specific 2-(2-hydroxyphenyl)-1,3,5-triazines are, for example,2,4-bis(biphenyl-4-yl)-6-(2,6-dihydroxy)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-diphenyl1,3,5-triazine,2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Particularly preferred are UV-light absorbers selected from the groupconsisting of (2,4di-hydroxyphenyl)-phenylmethanone,2-benzotriazol-2-yl-4methylphenol, 4-benzotriazol-2-ylbenzene-1,3-diol,3-[3-tert.-butyl-5-(5-chlorobenzotriazol-2-yl)-4hydroxyphenyl]-propionicacid, 3-[5-(benzotriazol-2-yl)-3-tert.-butyl-4-hydroxyphenyl]propionicacid; 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene1,3-diol,4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,4-[4,6-di-(2,4-di-hydroxyphenyl)-1,3,5-triazin2-yl]-benzene-1,3-diol andN′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide.

A preferred embodiment of the invention relates to a compound (I),wherein

-   -   a) A and Z represent chain terminal groups from a mono-(r=1),        di-(r=2) or trifunctional (r=3) chain transfer agent A(—Z)_(r);        -   r represents a numeral from one to three;        -   B and B′ independently of one another represent an            unsaturated or hydrogenated repeating unit from cycloolefins            polymerised by metathesis selected from the group consisting            of cyclopropene, cyclobutene, cyclopentene, cycloheptene,            cyclooctene, cyclopentadiene, dicyclopentadiene,            cyclohexadiene, cycloheptadiene, cyclooctadiene,            norbornadiene, norbornene and norbornene derivatives; and        -   X, X′, Y, Y′, p, p′, q and q′ are as defined above; or            wherein    -   b) q and q′ represent zero;        -   A and Z represent chain terminal groups from a mono- (r=1),            di- (r=2) or trifunctional (r=3) chain transfer agent            A(—Z)_(r); wherein            -   A represents the chain terminal group Y″—X″—, wherein            -   Y″ represents a UV-light absorber moiety; and            -   X″ represents a bivalent group; and        -   B, B′, p, p′ and r are as defined above under a).

Another preferred embodiment of the invention relates to a compound (I),wherein

-   -   a) one of q and q′ represents zero, one or a numeral greater        than one and the other one represents a numeral greater than        one;        -   A and Z represent chain terminal groups from a mono- (r=1),            di- (r=2) or trifunctional (r=3) chain transfer agent            A(—Z)_(r);        -   r represents a numeral from one to three;        -   B and B′ independently of one another represent an            unsaturated or hydrogenated repeating unit from cycloolefins            polymerised by metathesis selected from the group consisting            of cyclopropene, cyclobutene, cyclopentene, cycloheptene,            cyclooctene, cyclopentadiene, dicyclopentadiene,            cyclohexadiene, cycloheptadiene, cyclooctadiene,            norbornadiene, norbornene and norbornene derivatives;        -   X and X′ independently of one another represent bivalent            groups selected from the group consisting of —O—, —O—C(═O)—,            —C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene;        -   Y and Y′ independently of one another represent a UV-light            absorber moiety selected from the group consisting of            2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones,            benzoic acid esters, oxanilides and            2-(2-hydroxyphenyl)-1,3,5-triazines; and        -   p and p′ are as defined above; or wherein    -   b) q and q′ represent zero;        -   A represents the chain terminal group Y″—X″—, wherein        -   Y″ represents a UV-light absorber moiety selected from the            group consisting of 2-(2′-hydroxyphenyl)benzotriazoles,            2-hydroxybenzophenones, benzoic acid esters, oxanilides and            2-(2-hydroxyphenyl)-1,3,5-triazines; and        -   X″ represents a bivalent group selected from the group            consisting of —O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)-            and C₁-C₈alkylene; and    -   B, B′, p, p′ and r are as defined above.

A highly preferred embodiment of the invention relates to a compound(I), wherein

-   -   a) one of q and q′ represents zero or a numeral greater than one        and the other one represents a numeral greater than one;        -   A and Z represent chain terminal groups from a mono- (r=1),            di- (r=2) or trifunctional (r=3) chain transfer agent            A(—Z)_(r);        -   r represents a numeral from one to three;        -   B and B′ independently of one another represent an            unsaturated or hydrogenated repeating unit from cycloolefins            polymerised by metathesis selected from the group consisting            of cyclopentadiene, dicyclopentadiene, norbornadiene,            norbornene and norbornene derivatives;        -   X and X′ independently of one another represent bivalent            groups selected from the group consisting of —O—, —O—C(═O)—,            —C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene;        -   Y and Y′ independently of one another represent a UV-light            absorber moiety selected from the group consisting of            (2,4-dihydroxyphenyl)-phenylmethanone,            2-benzotriazol-2-yl-4-methylphenol,            4-benzotriazol-2-ylbenzene-1,3-diol,            3-[3-tert.-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionic            acid,            3-[5-(benzotriazol-2-yl)-3-tert.-butyl-4-hydroxyphenyl]-propionic            acid, 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene-1,3-diol,            4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,            4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,            N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide; and        -   p and p′ are as defined above; or wherein    -   b) q and q′ represent zero;        -   A represents the chain terminal group Y″—X″—, wherein            -   Y″ represents a UV-light absorber moiety selected from                the group consisting of                (2,4-dihydroxyphenyl)-phenylmethanone,                2-benzotriazol-2-yl-4-methylphenol,                4-benzotriazol-2-ylbenzene-1,3-diol,                3-[3-tert.-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionic                acid,                3-[5-(benzotriazol-2-yl)-3-tert.-butyl-4-hydroxyphenyl]-propionic                acid,                4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene-1,3-diol,                4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,                4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,                N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide; and            -   X″ represents a bivalent group selected from the group                consisting of —O—, —O—C(═O)—, —C(═O)—O—,                —O(C₁-C₈alkylene)- and C₁-C₈alkylene; and        -   B, B′, p, p′ and r are as defined above.

Another highly preferred embodiment relates to a compound of the formula

-   -   wherein    -   q represents one;    -   p and p′ together represent a numeral from 2 to 20;    -   A represents a chain terminal group from an olefinic chain        transfer agent (CTA);    -   X represents a bivalent group selected from the group consisting        of —O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)- and        C₁-C₈alkylene; and    -   Y represents a UV-light absorber moiety selected from the group        consisting of 2-(2′-hydroxyphenyl)benzotriazoles,        2-hydroxybenzophenones, benzoic acid esters, oxanilides and        2-(2-hydroxyphenyl)-1,3,5-triazines; or wherein    -   q represents zero;    -   p and p′ together represent a numeral from 2 to 20; and    -   A represents the group Y—X—, wherein        -   X represents a bivalent group selected from the group            consisting of —O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)-            and C₁-C₈alkylene; and        -   Y represents a UV-light absorber moiety selected from the            group consisting of 2-(2′-hydroxyphenyl)benzotriazoles,            2-hydroxybenzophenones, benzoic acid esters, oxanilides and            2-(2-hydroxyphenyl)-1,3,5-triazines.

A particularly highly preferred embodiment of the invention relates to acompound of the formula:

-   -   wherein    -   r represents a numeral from one to three;    -   p and p′ together represent a numeral from 2 to 20;    -   X represents a bivalent group selected from the group consisting        of —O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)- and        C₁-C₈alkylene; and    -   Y represents a substituted phenolic group derived from UV-light        absorbers selected from the group consisting of        (2,4-dihydroxyphenyl)-phenylmethanone,        2-benzotriazol-2-yl-4-methylphenol,        4-benzotriazol-2-ylbenzene-1,3-diol,        3-[3-tert.-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionic        acid,        3-[5-(benzotriazol-2-yl)-3-tert.-butyl-4-hydroxyphenyl]-propionic        acid; 4-(4,6-diphenyl)1,3,5-triazin-2-yl-benzene-1,3-diol,        4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin2-yl]-benzene-1,3-diol,        4-[4,6-di-(2,4-di-hydroxyphenyl)-1,3,5-triazin2-yl]-benzene-1,3-diol,        4-[4,6-bis(4-hydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol        and N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide;

Another embodiment of the invention relates to a metathesis polymer ofthe formulaA—[B_(p)—(X—Y)_(q)]—A′  (I′),

-   -   wherein    -   A and A′ represent chain terminal groups from a chain transfer        agent (CTA);    -   B represents an unsaturated or hydrogenated repeating unit from        cycloolefins polymerised by metathesis;    -   X represents a bridge group which connects B with the        substituent Y;    -   Y represents the aromatic substituent of a UV-light absorber;    -   p represents a numeral greater than one and defines the number        of repeating units in the metathesis polymer; and    -   q represents one or a numeral greater than one and defines the        number of aromatic substituents Y attached with the bridge group        X to B.

Another preferred embodiment of the invention relates to a polymerisatecomprising a metathesis polymer (I′), wherein

-   -   A and A′ represent chain terminal groups from an olefinic chain        transfer agent (CTA);    -   B represents an unsaturated or hydrogenated repeating unit from        cycloolefins polymerised by metathesis selected from the group        consisting of cyclopropene, cyclobutene, cyclopentene,        cycloheptene, cyclooctene, cyclopentadiene, cyclohexadiene,        cycloheptadiene, cyclooctadiene, norbornadiene, norbornene and        norbornene derivatives;    -   X represents bivalent atoms or bridge groups selected from the        group consisting of —O—, —O—C(═O)— and —C(═O)—O—;    -   Y represents a substituted phenolic group of UV-light absorbers        selected from the group consisting of        2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones,        benzoic acid esters, oxanilides and        2-(2-hydroxyphenyl)-1,3,5-triazines;    -   p represents a numeral greater than ten; and    -   q represents one or a numeral greater than one.

Another particularly preferred embodiment of the invention relates to apolymerisate comprising a metathesis polymer (I′), wherein

-   -   A and A′ represent chain terminal groups from an olefinic chain        transfer agent (CTA);    -   B represents an unsaturated or hydrogenated repeating unit from        cycloolefins polymerised by metathesis selected from the group        the group consisting of cyclopentadiene, norbornadiene,        norbornene and norbornene derivatives;    -   X represents bivalent atoms or bridge groups selected from the        group consisting of —O—, —O—C(═O)— and —C(═O)—O—;    -   Y represents a substituted phenolic group of UV-light absorbers        selected from the group consisting of        (2,4-dihydroxyphenyl)-phenylmethanone,        2-benzotriazol-2-yl-4-methyl-phenol,        4-benzotriazol-2-ylbenzene-1,3-diol,        3-[3-tert.-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionic        acid,        3-[5-(benzotriazol-2-yl)-3-tert.-butyl-4-hydroxyphenyl]-propionic        acid, 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene-1,3-diol,        4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,        4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,        N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide;    -   p represents a numeral greater than ten; and    -   q represents one or a numeral greater than one.

A specifically preferred embodiment of the invention relates to apolymerisate comprising a metathesis polymer (I′), wherein

-   -   A and A′ represent chain terminal groups from an olefinic chain        transfer agent (CTA);    -   B represents a polymer fragment comprising repeating units from        cycloolefins polymerised by metathesis selected from the group        consisting of        norbornene-2,5-methoxy-carbonyl-norbornene-2,5-methyl-5-methoxycarbonyl-norbornene-2,5-cyanonorbornene-2,5-methyl-5-cyanonorbornene,        5,5-dicyano-norbornene2,1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octa-hydronapthaline,        6-methyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,        6-methyl-6-methoxycarbonyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,        6-methoxycarbonyl-1,4,5,8-dimethano1,4,4a,5,6,7,8,8a-octahydronapthaline,        6-cyano-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,        6-ethyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,        6-ethylidene-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,        6,7-dimethyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,        1,4-dimethano-1,4,4a,9a-tetra-hydrofluorene, dicyclopentadiene,        tricyclopentadiene, tetracyclopentadiene, tetracyclododecene and        methyl tetracyclododecene;    -   X represents bivalent atoms or bridge groups selected from the        group consisting of —O—, —O—C(═O)— and —C(═O)—O—;    -   Y represents a substituted phenolic group of UV-light absorbers        selected from the group consisting of        (2,4-dihydroxyphenyl)-phenylmethanone,        2-benzotriazol-2-yl-4-methylphenol,        4-benzotriazol-2-ylbenzene-1,3-diol,        3-[3-tert.-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionic        acid,        3-[5-(benzotriazol-2-yl)-3-tert.-butyl-4-hydroxyphenyl]-propionic        acid; 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene1,3-diol,        4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,        4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol        and N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide;    -   p represents a numeral greater than ten; and    -   q represents one or a numeral greater than one.

High preference is also given to a polymerisate comprising a metathesispolymer having the formula

-   -   wherein    -   A and A′ represent chain terminal groups from an olefinic chain        transfer agent (CTA);    -   X represents a bridge group which connects A′ with Y;    -   Y represents a substituted phenolic group of UV-light absorbers        selected from the group consisting of        2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones,        benzoic acid esters, oxanilides and        2-(2-hydroxyphenyl)-1,3,5-triazines;    -   r represents zero or one; and    -   n and n′ represent numerals greater than zero.

The present invention also relates to a polymerisable compositioncomprising

-   -   a) a catalytically effective amount of a penta- or hexavalent        ruthenium or osmium carbene catalyst capable of performing ring        opening metathesis polymerisation of cycloolefins; and    -   b) the chain transfer agent A(—Z)_(r) and monomers capable of        forming a compound of the formula        A—{[B_(p)—(X—Y)_(q)][B′_(p)—(X′—Y′)_(q′)]Z}_(r)  (I),        wherein A, B, B′ X, X′, Y, Y′, Z, r, p, p′, q and q′ are as        defined above.

A suitable penta- or hexavalent ruthenium or osmium carbene catalystpresent in the composition mentioned above is described on pages 12-44of Olefin Metathesis and Metathesis Polymerization; K. J. Ivin, J. C.Mol. Academic Press, ISBN 0-12-377045-9.

A particularly suitable penta- or hexavalent ruthenium or osmium carbenecatalyst is represented by the formulae:

-   -   wherein    -   Me represents ruthenium or osmium;    -   L_(a) and L_(b) independently of one another represent anionic        ligands;    -   L¹, L² and L³ independently of one another represent        monodentate, donor ligands; and    -   R represents aryl, arylthio, or C₃-C₅-alkenyl.

The anionic ligands L_(a) and L_(b) are, for example, hydride ions (H⁻)or are derived from inorganic or organic acids, examples being halides,e.g. F⁻, Cl⁻, Br⁻ or I⁻, fluoro complexes of the type BF₄ ⁻, PF₆ ⁻, SbF₆⁻ or AsF₆ ⁻, anions of oxygen acids, alcoholates or acetylides or anionsof cyclopentadiene.

The anions of oxygen acids can be, for example, sulphate, phosphate,perchlorate, perbromate, periodate, antimonate, arsenate, nitrate,carbonate, the anion of a C₁-C₈carboxylic acid, such as formate,acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- ortri-chloro- or -fluoroacetate, sulfonates, for example methylsulfonate,ethylsulfonate, propylsulfonate, butylsulfonate,trifluoromethylsulfonate (triflate), unsubstituted or C₁-C₄alkyl,C₁-C₄alkoxy or halogen, especially fluoro, chloro or bromo substitutedphenylsulfonate or benzylsulfonate, for example tosylate, mesylate,brosylate, p-methoxy- or p-ethoxyphenylsulfonate,pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate.

Particularly preferred anionic ligands L_(a) and L_(b) are H⁻, F⁻, Cl⁻,Br⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, CF₃SO₃ ⁻, C₆H₅—SO₃ ⁻,4-methyl-C₆H₄—SO₃ ⁻, 3,5-dimethyl-C₆H₃—SO₃ ⁻, 2,4,6-trimethyl-C₆H₂—SO₃ ⁻and 4-CF₃—C₆H₄—SO₃ ⁻ and also cyclopentadienyl (Cp⁻). Cl⁻ is especiallypreferred.

In the compounds of the formulae IIa and IIb up to three neutral ligandsfrom the group L¹, L² and L³ are tertiary-substituted phosphine having3- about 40, preferably 3-30 and, with particular preference, 3-18carbon atoms. The tertiary-substituted phosphine is preferably acompound of the formula

in which R¹, R² and R³ independently of one another are C₁-C₂₀alkyl,C₃-C₁₂cycloalkyl, C₂-C₁₁heterocycloalkyl, C₅-C₁₂aryl, C₁-C₁₂heteroarylor C₆-C₁₄aralkyl, where alkyl, cycloalkyl, heterocycloalkyl, aryl,heteroaryl and aralkyl are unsubstituted or substituted by one or moresubstituents of the group consisting of C₁-C₆alkyl, C₁-C₆alkoxy, C_(1-C)₆haloalkyl, C₅-C₁₂aryl, —NO₂, SO₃ ⁻, ammonium and halogen; the radicalsR¹ and R² together are unsubstituted or C₁-C₆alkyl-, C₁-C₆haloalkyl-,—NO₂— or C₁-C₆alkoxy-substituted tetra- or pentamethylene, which may befused to 1 or 2 1,2-phenylene radicals, and R³ is as defined above.

Particular preference is given to phosphines wherein R¹, R² and R³ aremethyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2- or3-pentyl, 1-, 2-, 3- or 4-hexyl, cyclopentyl, cyclohexyl, phenyl,naphthyl or benzyl, e.g. (i-C₃H₇)₃P, (C₅H₉)₃P and (C₆H₁₁)₃P.

In the compounds of the formulae IIa and IIb one or two neutral ligandsfrom the group L¹, L² and L³ are monodentate, neutral e⁻ donor ligandshaving electron donor properties, or two ligands from this grouptogether are bidentate, neutral e⁻ donor ligands.

Such ligands are derived from unsubstituted or substituted heteroarenesfrom the group consisting of furan, thiophene, pyrrole, pyridine,bis-pyridine, picolylimine, γ-pyran, γ-thiopyran, phenanthroline,pyrimidine, bis-pyrimidine, pyrazine, indole, coumarone, thionaphthene,carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole,benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole,quinoline, bis-quinoline, isoquinoline, bis-isoquinoline, acridine,chromene, phenazine, phenoxazine, phenothiazine, triazine, thian-threne,purine, bis-imidazole and bis-oxazole.

These ligands may further be substituted by suitable substituentsselected from the group consisting of C₁-C₆-alkyl, C₁-C₆alkoxy, carboxy,C₁-C₆alkoxycarbonyl, C₁-C₆haloalkyl, nitro, sulfo, ammonium and halogen.

Aryl and arylthio R is, for example, unsubstituted phenyl and phenylthioor phenyl and phenylthio which is substituted by one or moresubstituents from the group consisting of C₁-C₆-alkyl, C₁-C₆alkoxy,carboxy, C₁-C₆alkoxycarbonyl, C₁-C₆haloalkyl, nitro, sulfo, ammonium andhalogen.

C₃-C₅-alkenyl R is, for example, vinyl, 1-, 2- or 3-propenyl, or thedifferent butenyl, pentenyl or hexenyl isomers, 1,3-hexadienyl or2,4,6-heptatrienyl or is ethylidene, 1- or 2-propylidene or 1-, 2- or3-propylidene directly attached to the carbene group. These substituentsmay be substituted with additional substituents selected from the groupconsisting of halogen, C₁-C₅-alkoxy or phenyl which in turn may besubstituted with C₁-C₅-alkyl halogen or C₁-C₅-alkoxy.

The monomers and chain transfer agents can be present in an amount offrom 0.01 to 99% by weight, preferably from 0.1 to 95% by weight, withparticular preference from 1 to 90% by weight and, with especialpreference, from 5 to 80% by weight, based on the monomers present inthe composition.

The composition may comprise inert solvents. One particular advantage isthat in the case of liquid monomers metathesis polymerisation can becarried out without the use of a solvent. A further advantage is thatthe polymerisation can even be carried out in water, polar and proticsolvents or water/solvent mixtures.

Examples of suitable inert solvents are protic polar and aproticsolvents, which can be used alone or in mixtures of at least twosolvents. Examples are ethers (dibutyl ether, tetrahydrofuran, dioxane,ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethylor diethyl ether, diethylene glycol diethyl ether, triethylene glycoldimethyl ether), halogenated hydrocarbons, etc..

In the context of the present invention, catalytic amounts denotepreferably an amount from 0.001 to 1.0 mol-%, with particular preferencefrom 0.01 to 0.5 mol-% and, with very particular preference, from 0.01to 0.1 mol-%, based on the amount of monomer.

The composition of the invention can comprise additives suitable forpolymers, which additives are preferably used as formulating auxiliariesto improve together with the compounds of the formula (I) the chemicaland physical properties of the polymers containing these additives. Theauxiliaries can be present in high proportions, for example, in amountsof up to 70% by weight, preferably from 1 to 70% by weight, morepreferably from 5 to 60% by weight, with particular preference from 10to 50% by weight and with especial preference from 10 to 40% by weight,based on the composition. Such auxiliaries have been disclosed in largenumbers and are set out by way of example in the following list ofauxiliaries: antioxidants selected from the group consisting ofalkylated monophenols, alkylthiomethylphenols, hydroquinones andalkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers,alkylidene-bis-phenols, O-, N- and S-benzyl compounds, hydroxybenzylatedmalonates, aromatic hydroxybenzyl compounds, triazine compounds,benzylphosphonates, acylaminophenols, esters ofβ-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionic acid, esters ofβ-(3,5-di-tert.-butyl-4-hydroxy3-methylphenyl)propionic acid, esters ofβ-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, esters and amides of3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, ascorbic acid andaminic antioxidants, light stabilisers, phosphites, phosphines,phosponites, hydroxylamines, nitrones, thiosynergists, peroxidescavengers, polyamide stabilisers, basic co-stabilisers, nucleatingagents, fillers and reinforcing agents, plasticizers, lubricants,emulsifiers, pigments, rheological additives, levelling assistants,optical brighteners, flameproofing agents, antistatic agents, blowingagents, benzofuranones and indolinones.

Such auxiliaries have been disclosed in large numbers and are set out byway of example in the following list of auxiliaries:

-   1. Antioxidants-   1.1. Alkylated monophenols, for example    2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di-methylphenol,    2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,    2,6-di-tert-butyl-4-isobutylphenol,    2,6-dicyclopentyl-4-methylphenol,    2-(α-methylcyclohexyl)-4,6-di-methylphenol,    2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,    2,6-di-tert-butyl-4-methoxymethylphenol, linear or side    chain-branched nonylphenols; such as 2,6-dinonyl-4-methylphenol,    2,4-dimethyl-6-(1-methylundec-1′-yl)phenol,    2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,    2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.-   1.2. Alkylthiomethylphenols, for example    2,4-dioctylthiomethyl-6-tert-butylphenol,    2,4-dioctylthiomethyl-6-methylphenol,    2,4-dioctylthiomethyl-6-ethylphenol,    2,6-didodecylthiomethyl-4-nonylphenol.-   1.3. Hydroquinones and alkylated hydroquinones, for example    2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,    2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,    2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyphenyl stearate,    bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.-   1.4. Tocopherols, for example α-, β-, γ- or δ-tocopherol and    mixtures thereof (vitamin E).-   1.5. Hydroxylated thiodiphenyl ethers, for example    2,2′-thiobis(6-tert-butyl-4-methylphenol),    2,2′-thiobis(4-octylphenol),    4,4′-thiobis(6-tert-butyl-3-methylphenol),    4,4′-thiobis(6-tert-butyl-2-methylphenol),    4,4′-thiobis(3,6-di-sec-amylphenol),    4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulphide.-   1.6. Alkylidene-bis-phenols, for example    2,2′-methylene-bis(6-tert-butyl-4-methylphenol),    2,2′-methylenebis(6-tert-butyl-4-ethylphenol),    2,2′-methylene-bis[4-methyl-6-(α-methylcyclohexyl)phenol],    2,2′-methylene-bis(4-methyl-6-cyclohexylphenol),    2,2′-methylene-bis(6-nonyl-4-methylphenol),    2,2′-methylene-bis(4,6-di-tert-butylphenol),    2,2′-ethylidene-bis(4,6-di-tert-butylphenol),    2,2′-ethylidene-bis(6-tert-butyl-4-isobutylphenol),    2,2′-methylene-bis[6-(α-methylbenzyl)-4-nonylphenol],    2,2′-methylene-bis[6-(α,α-dimethylbenzyl)-4-nonylphenol],    4,4′-methylene-bis(2,6-di-tert-butylphenol),    4,4′-methylene-bis(6-tert-butyl-2-methylphenol),    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,    2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,    1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,    ethylene glycol    bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],    bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,    bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,    1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane,    2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,    2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,    1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.-   1.7. O—, N— and S-benzyl compounds, for example    3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxy-dibenzyl ether, octadecyl    4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl    4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,    tris(3,5-di-tert-butyl-4-hydroxybenzyl)-amine,    bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,    bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulphide, isooctyl    3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.-   1.8. Hydroxybenzylated malonates, for example dioctadecyl    2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl    2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecyl    mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,    di-[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.-   1.9. Aromatic hydroxybenzyl compounds, for example    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,    1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,    2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.-   1.10. Triazine compounds, for example    2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,    2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,    1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,    2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,    1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.-   1.11. Benzylphosphonates, for example dimethyl    2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, diethyl    3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl    3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl    5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt    of the monoethyl ester of    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.-   1.12. Acylaminophenols, for example 4-hydroxylauranilide,    4-hydroxystearanilide, octyl    N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.-   1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,    ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene    glycol, diethylene glycol, triethylene glycol, pentaerythritol,    tris(2-hydroxyethyl)isocyanurate, N,N′-bis(2-hydroxyethyl)oxalamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic    acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,    ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene    glycol, diethylene glycol, triethylene glycol, pentaerythritol,    tris(2-hydroxyethyl) isocyanurate,    N,N′-bis(2-hydroxyethyl)oxalamide, 3-thiaundecanol,    3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene    glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,    diethylene glycol, triethylene glycol, pentaerythritol,    tris(2-hydroxyethyl)isocyanurate,    N,N′-bis(2-hydroxyethyl)-oxalamide, 3-thiaundecanol,    3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with    mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,    octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,    1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene    glycol, triethylene glycol, pentaerythritol,    tris(2-hydroxyethyl)isocyanurate,    N,N′-bis(2-hydroxyethyl)-oxalamide, 3-thiaundecanol,    3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,    e.g.    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,    N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]-oxamide    (Naugard® XL-1 from Uniroyal).-   1.18. Ascorbic acid (vitamin C).-   1.19. Aminic antioxidants, for example    N,N′-diisopropyl-p-phenylenediamine,    N,N′-di-sec-butyl-p-phenylenediamine,    N,N′-bis(1,4-dimethyl-pentyl)-p-phenylenediamine,    N,N′-bis(1-ethyl-3-methyl-pentyl)-p-phenylenediamine,    N,N′-bis(1-methylheptyl)-p-phenylenediamine,    N,N′-dicyclohexyl-p-phenylenediamine,    N,N′-diphenyl-p-phenylenediamine,    N,N′-di-(2-naphthyl)-p-phenylenediamine,    N-isopropyl-N′-phenyl-p-phenylenediamine,    N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,    N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,    N-cyclohexyl-N′-phenyl-p-phenylenediamine,    4-(p-toluenesulfonamido)-diphenylamine,    N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,    N-allyldiphenylamine, 4-isopropoxydiphenylamine,    N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,    N-phenyl-2-naphthylamine, octylated diphenylamine, for example    p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,    4-butyrylaminophenol, 4-nonanoylaminophenol,    4-dodecanoylaminophenol, 4-octadecanoylaminophenol,    di-(4-methoxyphenyl)amine,    2,6-di-tert-butyl-4-dimethylaminomethylphenol,    2,4′-diamino-diphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,    N′-tetramethyl-4,4′-diamino-diphenylmethane,    1,2-di[(2-methylphenyl)amino]ethane, 1,2-di(phenylamino)-propane,    (o-tolyl)biguanide, di-[4-(1′,3′-dimethylbutyl)phenyl]amine,    tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and    dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-    and dialkylated nonyldiphenylamines, a mixture of mono- and    dialkylated dodecyldiphenylamines, a mixture of mono- and    dialkylated isopropyl/isohexyl-diphenylamines, mixtures of mono- and    dialkylated tert-butyldiphenylamines,    2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a    mixture of mono- and dialkylated    tert-butyl/tert-octyl-phenothiazines, a mixture of mono- and    dialkylated tert-octyl-phenothiazines, N-allylphenothiazine,    N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,    N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethyienediamine,    bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,    2,2,6,6-tetramethylpiperidin-4-one and    2,2,6,6-tetramethylpiperidin-4-ol.-   2. Other UV-Absorbers and Light Stabilisers-   2.1. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate or    isooctyl α-cyano-β,β-diphenylacrylate, methyl    α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate    or butyl α-cyano-β-methyl-p-methoxycinnamate, methyl    α-carbomethoxy-p-methoxycinnamate and    N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.-   2.2. Nickel compounds, for example nickel complexes of    2,2′-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1-    or 1:2-complex, with or without additional ligands such as    n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel    dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of    the methyl or ethyl ester, of    4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes    of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecyl ketoxime,    nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or    without additional ligands.-   2.3. Sterically hindered amines, for example    bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,    bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate,    bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,    bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,    bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,    the condensate of    1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic    acid, the linear or cyclic condensates of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,    tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,    tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetraoate,    1,1′-(1,2-ethane-diyl)-bis(3,3,5,5-tetramethylpiperazinone),    4-benzoyl-2,2,6,6-tetramethylpiperidine,    4-stearyloxy-2,2,6,6-tetramethylpiperidine,    bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,    3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro-[4.5]decane-2,4-dione,    bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,    bis(1-octyl-oxy-2,2,6,6-tetramethylpiperidyl)succinate, the linear    or cyclic condensates of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of    2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-aminopropylamino)ethane, the condensate of    2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-amino-propylamino)ethane,    8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,    3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,    3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,    a mixture of 4-hexadecyloxy- and    4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and    4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of    1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine    and also 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.    [136504-96-6]);    N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,    N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,    2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane,    the reaction product of    7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane    and epichlorohydrine,    1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ether,    N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine,    the diester of 4-methoxymethylene-malonic acid with    1,2,2,6,6-pentamethyl-4-hydroxypiperidine,    poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,    the reaction product of maleic anhydride-α-olefin copolymer and    2,2,6,6-tetramethyl-4-aminopiperidine or    1,2,2,6,6-pentamethyl-4-aminopiperidine.-   2.4. Oxalamides, for example 4,4′-dioctyloxyoxanilide,    2,2′-diethoxy-oxanilide,    2,2′-dioctyloxy-5,5′-di-tert-butyloxanilide,    2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide,    2-ethoxy-2′-ethyloxanilide,    N,N′-bis(3-dimethylaminopropyl)oxalamide,    2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with    2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of o- and    p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.-   2.5. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example    2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-octyloxyphenyl)-4,6bis(2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-di-methylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,    2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,    2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,    2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,    2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.-   3. Metal deactivators, for example, N,N′-diphenyloxalamide,    N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)-hydrazine,    3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl    dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl    bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide,    N,N′-bis(salicyloyl)oxalyl dihydrazide,    N,N′-bis(salicyloyl)thiopropionyl dihydrazide.-   4. Phosphites, phosphines and phosphonites, for example triphenyl    phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites,    tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl    phosphite, trimethylphosphine, tri-n-butylphosphine,    triphenylphosphine, distearyl pentaerythritol diphosphite,    tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol    diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol    diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol    diphosphite, bisisodecyloxypentaerythritol diphosphite,    bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,    bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite,    tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)    4,4′-biphenylene diphosphonite,    6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin,    6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin,    bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,    bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,    2,2′,2″-nitrilo[triethyl-tris-(3,3′,5,5″tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],    2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

Particular preference is given to using the following phosphites:Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba SpecialtyChemicals), tris(nonylphenyl) phosphite and the phosphites selected fromthe group comprising the structural formulae (A), (B), (C), (D), (E),(F) and (G) given below:

-   5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,    N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,    N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,    N,N-dihexadecylhydroxylamine, N,N-ditetradecylhydroxylamine,    N-hexadecyl-N-octadecylhydroxylamine,    N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine from    hydrogenated tallow fatty amines.-   6. Nitrones, for example N-benzyl α-phenyl nitrone, N-ethyl α-methyl    nitrone, N-octyl α-heptyl nitrone, N-lauryl α-undecyl nitrone,    N-tetradecyl α-tridecyl nitrone, N-hexadecyl α-pentadecyl nitrone,    N-octadecyl α-heptadecyl nitrone, N-hexadecyl α-heptadecyl nitrone,    N-octadecyl α-pentadecyl nitrone, N-heptadecyl α-heptadecyl nitrone,    N-octadecyl α-hexadecyl-nitrone, and nitrones derived from    N,N-dialkylhydroxylamines prepared from hydrogenated tallow fatty    amines.-   7. Thiosynergists, for example dilauryl thiodiproprionate or    distearyl thiodipropionate.-   8. Peroxide scavengers, for example esters of β-thiodipropionic    acid, for example the lauryl, stearyl, myristyl or tridecyl esters,    mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole,    zinc dibutyldithiocarbamate, dioctadecyl disulphide, pentaerythritol    tetrakis(β-dodecylmercapto)propionate.-   9. Polyamide stabilisers, for example copper salts in combination    with iodides and/or phosphorus compounds and salts of divalent    manganese.-   10. Basic co-stabilisers, for example melamine,    polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea    derivatives, hydrazine derivatives, amines, polyamides,    polyurethanes, alkali metal salts and alkaline earth metal salts of    higher fatty acids, for example calcium stearate, zinc stearate,    magnesium behenate, magnesium stearate, sodium ricinoleate,    potassium palmitate, antimony pyrocatecholate or zinc    pyrocatecholate.-   11. Nucleating agents, for example inorganic substances, such as    talc, metal oxides such as titanium dioxide or magnesium oxide,    phosphates, carbonates or sulphates of, preferably, alkaline earth    metals; organic compounds such as mono- or polycarboxylic acids and    their salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenyl    acetic acid, sodium succinate or sodium benzoate, and polymeric    compounds, for example ionic copolymers (ionomers).-   12. Fillers and reinforcing agents, for example calcium carbonate,    silicates, glass fibres, glass beads, talc, kaolin, mica, barium    sulphate, metal oxides and hydroxides, carbon black, graphite, wood    flour and flours or fibres of other natural products, and synthetic    fibres.-   13. Other additives, for example plasticizers, lubricants,    emulsifiers, pigments, rheological additives, catalysts, levelling    assistants, optical brighteners, flameproofing agents, antistatic    agents, blowing agents.-   14. Benzofuranones and indolinones, as described, for example, in    U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No.    5,175,312, U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4    316 611; DE-A-4 316 622; DE-A-4 316 876; EP-A-0 589 839 or EP-A-0    591 102, or    3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,    5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,    3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]-phenyl)benzofuran-2-one],    5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,    3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,    3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,    3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,    3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

Another preferred embodiment of the invention relates to a polymerisablecomposition comprising

-   -   a) a catalytically effective amount of a penta- or hexavalent        ruthenium or osmium carbene catalyst of the formulae:        -   wherein        -   Me represents ruthenium;        -   L_(a) and L_(b) independently of one another represent            anionic ligands;        -   L¹, L² and L³ independently of one another represent            monodentate, neutral e⁻ donor ligands;        -   R represents aryl, arylthio or C₃-C₅-alkenyl; and        -   b) the chain transfer agent A(—Z)_(r) and monomers capable            of forming the compound (I), wherein A, B, B′X, X′, Y, Y′,            Z, r, p, p′, q and q′ are as defined in claim 1.

A particularly preferred embodiment of the invention relates to apolymerisable composition comprising

-   -   a) a catalytically effective amount of a penta- or hexavalent        ruthenium carbene catalyst selected from the group consisting of    -   b) the chain transfer agent A(—Z)_(r) and monomers capable of        forming the compound (I), wherein A, B, B′ X, X′, Y, Y′, Z, r,        p, p′, q and q′ are as defined above.

The invention also relates to a process for preparing the compound (I)comprises applying the reaction conditions of Ring Opening MetathesisPolymerisation (=ROMP) to the polymerisable composition mentioned above.The invention also provides the polymers obtainable by the process ofthe invention.

The process for preparing the compound (I) is illustrated by thefollowing reaction sequences:

The process is preferably carried out at a temperature of at least 0° C.In particular, the process of the invention is conducted at temperaturesfrom 0° to 300° C., preferably at from room temperature to 250° C., withparticular preference from room temperature to 200° C. and, with specialpreference, from room temperature to 160° C.

Chain transfer agents to which UV-light absorber moieties are attached,particularly chain transfer agents according to the embodiment b), maybe prepared by attachment of a vinylic moiety to the UV-light absorberstructure, e.g. by etherifying a hydroxy group with an open chainalkene, e.g. allyl chloride or bromide, which may then by followed by aClaisen rearrangement.

A representative reaction sequence illustrating the preparation of thechain transfer agent is given below:

The selective alkylation of one hydroxy group is due to the differencebetween the pK_(a) of the two hydroxy groups. The reaction can becarried out in suitable solvents such as toluene, xylene, benzeneacetone, methylethyl ketone, methanol, ethanol, isopropanol,tert-amyl-alcohol, dimethylacetamide, preferred acetone, methanol anddimethylacetamide in the presence of suitable bases, such as sodiumhydroxide, potassium hydroxide, sodium carbonate potassium carbonate,pyridine triethylamine; preferably potassium carbonate. A preferredtemperature range is from 0 to 200° C., preferably under refluxconditions.

In another reaction sequence as shown below the allylation step isperformed as reported above followed by a thermal rearrangement, knownas Claisen rearrangement (J. March Advanced Organic Chemistry; FourthEdition; John Wiley & Sons). The rearrangement is preferably carried outin dimethylacetamide at 170° C.:

Branched (“polyfunctionalised” chain transfer agents (r=2, 3 or 4) canbe synthesised according to the following representative reactionsequence:

Depending on the nature and amount of the monomers used, the compoundsor oligomers of the invention may have different properties. Thecompounds prepared from the polymerisable compositions show a longerpersistency, due to their excellent compatibility with any polymericsubstrate and their appropriate molecular weight, that avoids anyadditive loss caused by thermal effects.

Another embodiment of the invention relates to a composition comprising

-   -   α) a composition of matter susceptible to degradation induced by        light, heat or oxidation; and    -   β) the compound (I), wherein A, B, B′ X, X′, Y, Y′, Z, r, p, p′,        q and q′ are as defined above.

A particularly preferred embodiment of the invention relates to acomposition comprising

-   -   α) a composition of matter susceptible to degradation induced by        light, heat or oxidation selected from the group consisting of        LDPE (=low density polyethylene), LLDPE (=linear low density        polyethylene),EVA (=ethylene vinyl acetate), PP (=polypropylene)        and PET (=polyethyleneterephthalate); and    -   β) the compound (I), wherein A, B, B′ X, X′, Y, Y′, Z, r, p, p′,        q and q′ are as defined above.

The additives or auxiliaries listed above selected from the groupconsisting of antioxidants, UV-absorbers, light stabilisers, metaldeactivators, phosphites, phosphines, phosphonites, hydroxylamines,nitrones, thiosynergists, peroxide scavengers, polyamide stabilisers,basic co-stabilisers, nucleating agents, fillers, reinforcing agents,benzofuranones, indolinones and other additives are present as optionalcomponents in the composition.

The polymers and compositions obtainable in accordance with theinvention are particularly suitable for producing structural polymers,wherein protection against UV-radiation is desirable, such as protectivefoils for greenhouses, packaging foils, mouldings for cars, boats,leisure articles, pallets, pipes, sheets, etc.

The present invention, therefore, also relates to a method forstabilising a composition of matter against degradation induced bylight, heat or oxidation, which comprises incorporating within thecomposition of matter the compound (I), wherein A, B, B′ X, X′, Y, Y′,Z, r, p, p′, q and q′ are as defined above.

In particular, the present invention relates to a method for selectivelyscreening the light radiation to which plants are exposed within greenhouses, which comprises incorporating within film material the compound(I), wherein A, B, B′ X, X′, Y, Y′, Z, r, p, p′, q and q′ are as definedabove.

In addition, the present invention relates to a method for selectivelyscreening the light radiation to which packed food is exposed, whichcomprises incorporating within a film material the compound (I), whereinA, B, B′ X, X′, Y, Y′, Z, r, p, p′, q and q′ are as defined above.

The following examples illustrate the invention without limiting thescope thereof:

Materials and Methods

In the following examples, the molecular weight parameters (M_(n),M_(w), PDI) is determined by GPC (Gel Permeation Chromatography). TheGPC measurements are carried out on a Perkin Elmer LC 50 liquidchromatograph equipped with a reflective index Perkin Elmer LC 30 andthe data are calculated by using a Perkin Elmer software (TurboSEC). AllGPC measurements are carried out by using 0.02 M di-ethanol-aminesolution in chromatographic grade tetrahydrofuran (THF) as solvent at45° C. The columns used are PLGEL (Polymer Laboratories) 300 mm×7.5 mm,stationary phase 3 m Mixed E , supplied by Polymer Laboratories.Polystyrene standards are used for the calibration curve.

Visual melting points and melting ranges are measured by using aGallenkamp equipment.

The extinction coefficients (ε) are calculated by recording theUV-spectra of the products in CH₂Cl₂ or toluene solutions on a PerkinElmer Lambda 2S spectrophotometer. Elemental analysis is carried out byusing a Perkin Elmer 2400-CHN equipment. The ¹H-NMR spectra are recordedat 300 MHz and 22° C. in CDCl₃, by using a Bruker AMX300 NMRspectrometer.

The indices m and n correspond to the indices p and p′ used and definedin the other parts of the description of the present invention.

EXAMPLE 1

1.1 Preparation of the Hydrogenated Oligomer as Represented by theFormula

To a solution of 45 g (0.0014 mol) of the polymer of Example 1.2 in 100ml of toluene, 0.4 g of platinum on carbon (10% W/W) are added. Themixture is poured into an auto-clave and hydrogenated for 24 hours at 65bar (p_(H2)) and 105° C. The mixture is filtered off and the solutionconcentrated under vacuum. A pale yellow powder is received.

Visual melting range: 92-97° C.; M_(n): 3300; M_(w): 6000; PDI: 1.82; ε(290 nm, CH₂Cl₂): 14856;

Elemental analysis:

% C % H % O theory 78.4 7.1 14.5 found 78.0 7.3 14.71.2 Preparation of the Oligomer of the Formula

44.6 g (0.14 mol) of the compound of Example 1.3.1 and 1.17 g (0.014mol) of 1-hexene are added to 450 ml toluene. 0.09 g (0.13 mmol) of thecatalystbis(tricyclopentylphosphine)dichloro(3-methyl-2-butenylidene)ruthenium(APT Cat ASMC 716) are added to the stirred solution and heated to 35°C. for 4 hours. The reaction mixture is then concentrated in the vacuum.A pale brown solid having a melting range of 88-94° C. is received.

Visual melting range: 102-107° C.; M_(n): 3100; M_(w): 5900; PDI: 1.90;ε (290 nm, CH₂Cl₂): 14521;

Elemental analysis:

% C % H % O theory 78.9 6.5 14.6 found 78.5 6.7 14.81.3 The Starting Materials are Prepared as Follows1.3.1 Preparation of

A solution of 250 g (1.0 mol) of the compound of Example 1.3.2 and 528 g(4.0 mol) of dicyclopentadiene in 1 l of mesitylene is refluxed for 24hours. The mixture is cooled to room temperature and concentrated in thevacuum to recover any excess of dicyclopentadiene. The crude product isrecrystallized from methanol.

Melting point: 105° C.; ¹H NMR (300 MHz, CDCl₃): δ=12.6 (s, 1 H),7.8-6.2 (aromatic signals 8H), 6.0 (m, 2H), 3.8 (m, 2H).1.3.2 Preparation of

A solution of 214 g (1.0 mol) of 2,4-dihydroxybenzophenone, 121 g (1.0mol) of allylbromide and 165 g (1.2 mol) of potassium carbonate in 500ml of acetone are refluxed for 7 hours. The mixture is then filtered offand the solution concentrated in the vacuum. A pale yellow powder isrecovered.

Melting point: 67° C.; ¹H NMR (300 MHz, CDCl₃): δ=12.5 (bs, 1H), 8.0-7.5(aromatic signals, 8H), 6.2 (m, 1H), 5.3 (m, 2H), 4.6 (m, 2H).

1.4 Application Example

In order to evaluate the UV-absorber characteristics of the polymer soobtained, when mixed with a commercial thermoplastic material, thin lowdensity polyethylene (LDPE) films are prepared, containing, as a typicalformulation, 0.8% by weight of the polymer. To do so, the polymerprepared as described in 1.2 is mixed with LDPE pellets (Riblene® FF 29,Enichem, Milano, Italy), characterised by a density of 0.921 g/cm³ and amelt flow index (190° C./2.1 kg of 0.6) in a turbo mixer. The mixture isextruded at a maximum temperature of 200° C. in a OMC twin-screwextruder. The granules so obtained are blown in a lab scale Formac®blow-extruder at a maximum temperature of 210° C. to give a film of 150μm thickness. UV-Vis spectra are recorded in the range of 200-800 nm bymeans of a Perkin-Elmer lambda 20 spectrophotometer, equipped with aRSA-PE-20 Labsphere integrating sphere. The film displays a strongabsorption band in the range 280-360 nm. In particular, transmittancevalues below 3% are detected between 280 and 350 nm.

Another piece of film of the same composition is also exposed in aforced circulating air oven at 60° C., in order to evaluate thepersistency of the polymer in LDPE. UV-Vis spectra are periodicallymeasured on the exposed sample. The maximum absorbance value in therange 280-360 nm is taken as a measure of the persistency, possiblyendangered by exposure of the film at high temperatures. The mainfinding is that no decrease of the absorbance value at maximum isobserved after 5000 hours at 60° C.

EXAMPLE 2

2.1 Preparation of a Hydrogenated Oligomer of the Formula

To a solution of 26.6 g (8.3 mmol) of the unsaturated polymerisate ofExample 2.2 in 100 ml of toluene, 0.3 g of platinum on carbon (10% w/w)is added. The mixture is poured into an autoclave and hydrogenated for24 hours at 65 bar (p_(H2)) and 105° C. The mixture is filtered off andthe solution concentrated under vacuum. A pale yellow powder isobtained.

Visual melting range: 58-62° C.; M_(n): 3400; M_(w): 6290; PDI: 1.85; ε(290 nm, CH₂Cl₂): 13254;

Elemental analysis:

% C % H % O theory 80.4 8.4 11.2 found 80.0 8.5 11.52.2 Preparation of the Oligomer of the Formula

20.0 g (0.062 mol) of the compound of Example 1.3.1 and 5.9 g (0.062mol) of norbornylene with 0.7 g (8.3 mmol) of 1-hexene are added to 450ml of toluene. 0.09 g (0.13 mmol) of the catalystbis(tricyclopentylphosphine)dichloro(3-methyl-2-butenylidene)ruthenium(APT Cat ASMC 716) are added to the stirred solution and heated to 35°C. for 4 hours. The reaction mixture is then concentrated in the vacuum.A pale brown solid having a melting range of 86-90° C. is received.

Visual melting range: 86-90° C.; M_(n): 3420; M_(w): 6975; PDI: 2.04; ε(290 nm, CH₂Cl₂): 14958;

Elemental analysis:

% C % H % O theory 81.2 7.5 11.3 found 80.8 7.6 11.62.3 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4, containing 0.8% by weight of the polymer. UV-Vis spectraare recorded as described in Example 1.4. The film displays a strongabsorption band in the range 280-360 nm. Transmittance values below 3%are detected between 280 and 350 nm. The persistency of the polymer inLDPE films is determined after exposure of the films at 60° C. andevaluated as described in Example 1.4. No decrease of the absorbancevalue at the maximum is observed after 4000 hours at 60° C.

EXAMPLE 3

3.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Example 1.1 the hydrogenated oligomer isobtained as a pale brown powder. Melting range: 92-97° C.; M_(n): 2800.3.2 Preparation of the Oligomer of the Formula

50.0 g (0.160 mol) of the compound of Example 1.3.1 and 5.0 g (0.02 mol)of the compound of Example 1.3.2 are added to 450 ml of toluene. 0.08 g(0.13 mmol) of the catalystbis(triisopropylphosphine)dichlorovinylsulphanylruthenium are added tothe stirred solution which is heated to 35° C. for 4 hours. The reactionmixture is then concentrated in the vacuum and a pale brown solid isreceived.

Visual melting range: 88-94° C.; M_(n): 1810; M_(w): 3440; PDI; 1.90; ε(290 nm, CH₂Cl₂);15734;

Elemental Analysis:

% C % H % O theory 78.3 6.2 15.5 found 77.2 6.3 16.5

EXAMPLE 4

4.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Example 1.1 a hydrogenated polymerisate isobtained as a pale brown powder. Visual melting range: 87-90° C.; M_(n):2300; M_(w): 4870; PDI: 2.11; ε (290 nm, CH₂Cl₂): 15987

Elemental Analysis:

% C % H % O % N theory 77.5 6.8 13.9 1.8 found 76.4 7.0 14.9 1.74.2 Preparation of the Oligomer of the Formula

In a manner analogous to Example 1.2 a polymerisate is obtained as apale brown powder by using the compound of Example 4.3.1 as the chaintransfer agent.

Visual melting range: 100-108° C.; M_(n): 2000; M_(w): 3300; PDI: 1.65;

Elemental Analysis:

% C % H % O % N theory 77.9 6.2 13.8 2.1 found 77.2 6.4 14.4 2.04.3 The Starting Materials are Prepared as Follows4.3.1 Preparation of

A solution of 110.0 g (0.40 mol) of the compound of Example 4.3.2 in 200ml of N,N-di-methylacetamide is heated to 170° C. for 16 hours. Thesolution is cooled and concentrated in the vacuum. A pale yellow powderis received.

¹H NMR (300 MHz, CDCl₃): δ=11.1 (s, 1H), 8.2-6.8 (aromatic signals, 6H),6.1 (m, 1H), 4.9 (m, 2H), 3.2 (m, 2H), 2.3 (s, 3H).4.3.2 Preparation of

In a manner analogous to Example 1.2.3 an orange oil is obtained fromthe starting materials Tinuvin® P and allyl bromide.

¹H NMR (300 MHz, CDCl₃): δ=8.1-6.9 (aromatic signals, 7H), 5.9 (m, 1H),5.1 (d, 1H), 4.9 (d, 1H), 4.5 (m, 2H), 2.3 (s, 3H).

4.4 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4, containing 0.8% by weight of the polymer. UV-Vis spectraare recorded as described in Example 1.4. The film displays a strongabsorption band in the range 280-360 nm. Transmittance values below 3%are detected between 280 and 340 nm. The persistency of the polymer inLDPE films is determined after their exposure at 60° C. and evaluated asdescribed in Example 1.4. No decrease of the absorbance value at maximumis observed after 2600 hours at 60° C.

EXAMPLE 5

5.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Examples 2.1 and 2.2 a pale yellow powder isobtained by using the compound of Example 5.2 as the chain transferagent.

Visual melting range: 100-110° C.: M_(n): 2700; M_(w): 5750; PDI: 2.13;ε (290 nm, CH₂Cl₂): 21805

Elemental Analysis:

% C % H % O % N theory 80.4 7.6 10.5 1.5 found 79.2 7.5 11.7 1.65.2 Preparation of the Starting Material of the Formula

In a manner analogous to Example 1.3.2 a white powder is obtained fromthe starting material:4-(4,6-bis-biphenyl-4-yl-(1,3,5)triazin-2-yl)-benzene-1,3-diol and allylbromide.

¹H NMR (300 MHz, CDCl₃): δ=13.3 (s, 1H), 8.7-6.2 (aromatic signals,21H), 6.1 (m, 1H), 5.3 (m, 2H), 4.3 (m, 2H).

5.3 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4, containing 0.6% by weight of the polymer. UV-Vis spectraare recorded as described in Example 1.4. The film displays a strongabsorption band in the range 280-360 nm. Transmittance values below 3%are detected between 280 and 350 nm. The persistency of the polymer inLDPE films is determined after their exposure at 60° C. and evaluated asdescribed in Example 1.4. No decrease of the absorbance value at maximumis observed after 1700 hours at 60° C.

EXAMPLE 6

6.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Examples 1.1 and 1.2 a pale yellow powder(melting range: 164-179° C. M_(n): 2000) is obtained by using thecompound of Example 6.2 as a monomer.

Visual melting range: 164-169° C.; M_(n): 2080; M_(w): 3080; PDI: 1.48;ε (317 nm, CH₂Cl₂): 68006;

Elemental Analysis:

% C % H % O % N theory 81.6 6.3 5.4 6.7 found 79.3 6.2 8.0 6.56.2. Preparation of the Starting Material of the Formula

In a manner analogous to Example 1.3.1 a white powder is obtained fromthe starting material of Example 5.2.

¹H NMR (300 MHz, CDCl₃): δ=13.2 (s, 1H), 8.9-6.8 (aromatic signals,21H), 6.1 (m, 2H).

6.3 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4, containing 0.4% by weight of the polymer. UV-Vis spectraare recorded as described in Example 1.4. The film displays a strongabsorption band in the range 280-360 nm. Transmittance values below 3%are detected between 300 and 340 nm. The persistency of the polymer inLDPE films is determined after their exposure of the films at 60° C. andevaluated as described in Example 1.4. No decrease of the absorbancevalue at maximum is observed after 4000 hours at 60° C.

EXAMPLE 7

7.1 Preparation of

In a manner analogous to Examples 1.1 and 1.2 a pale yellow powder(melting range: 143-151° C., M_(n): 2800) is obtained by using thecompound of Example 7.2.2 as the chain transfer agent.

Visual melting range: 143-151° C.; M_(n): 2000; M_(w): 3200; PDI: 1.60;ε (290 nm, CH₂Cl₂): 39267;

Elemental analysis:

% C % H % O % N theory 77.1 5.9 8.2 8.8 found 76.5 6.2 8.1 9.27.2 The Starting Materials are Prepared as Follows7.2.1 Preparation of

In a manner analogous to Example 1.2.2 a white powder (melting range151-161° C.) is obtained from the starting material of Example 7.2.2.

Visual melting range: 151-161° C.; ¹H NMR (300 MHz, CDCl₃): δ=12.6 (s,1H), 8.5-7.5 (aromatic signals, 13H), 6.5 (m, 2H), 3.9 (m, 2H).7.2.2 Preparation of

In a manner analogous to Example 1.2.3 a white solid (melting range171-181° C.) is obtained from4-(4,6-diphenyl-(1,3,5)triazin-2-yl)-benzene-1,3-diol and allyl bromide.

Visual melting range: 171-181° C.; ¹H NMR (300 MHz, CDCl₃): δ=13.6 (s,1H), 8.5-7.5 (aromatic signals, 13H), 6.6 (m, 1H), 5.4 (m, 2H), 4.5 (m,2H).

7.3 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4 containing 0.4% by weight of the polymer. UV-Vis spectra arerecorded as described in Example 1.4. The film displays a strongabsorption band in the range 280-360 nm. Transmittance values below 3%are detected between 280 and 340 nm. The persistency of the polymer inLDPE films is determined after their exposure at 60° C. and evaluated asdescribed in Example 1.4. No decrease of the absorbance value at maximumis observed after 4000 hours at 60° C.

EXAMPLE 8

8.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Examples 2.1 and 2.2 a pale yellow powder isobtained by using the product of Example 8.2.1 as the monomer and theproduct of Example 8.2.2 as the chain transfer agent.

Visual melting range: 80-90° C.; M_(n): 2600; M_(w): 6340; PDI: 2.44; ε(290 nm, CH₂Cl₂): 9074;

Elemental analysis:

% C % H % O % N % Cl theory 69.5 7.4 8.9 7.7 6.5 found 70.9 7.7 9.3 6.75.48.2 The Starting Materials are Prepared as Follows8.2.1 Preparation of

In a manner analogous to Example 1.3.1 a white solid is obtained fromthe starting material of Example 8.2.2.

Visual melting range: 35-39° C.; ¹H NMR (300 MHz, CDCl₃): δ=11.5 (s,1H), 8.3-7.1 (aromatic signals, 5H), 6.1 (m, 2H), 3.9 (m, 2H), 1.5 (s,9H).8.2.2 Preparation of

75.0 g (0.193 mol) of3-(3-tert-butyl-5-(5-chloro-benzotriazol-2-yl)-4-hydroxy-phenyl)-propionicacid methyl ester and 30.0 g (0.517 mol) of allyl alcohol and 0.3 g (1.6mmol) of PTSA are dissolved in 250 ml of toluene. The mixture is pouredin an autoclave and heated at 110° C. for 24 hours. The organic layer iswashed with water, dried under anhydrous sodium sulphate and evaporatedunder vacuum. A white powder is obtained.

¹H NMR (300 MHz, CDCl₃): δ=12.0-10.0 (bs, 1H), 8.4-7.4 (aromaticsignals, 5H), 5.9 (m, 1H), 5.3 (m, 2H), 4.6 (m, 2H), 3.0 (m, 2H), 2.7(m, 2H), 1.5 (s, 9H).

8.3 Application Example

In order to evaluate the UV-absorber characteristics of the compound soobtained, when mixed with a commercial thermoplastic material, thinlinear low density polyethylene (LLDPE) films are prepared, containing,as a typical formulation, 1% by weight of the compound. To do so, thepolymer prepared as described in 8.1 is mixed with milled LLDPE (Dowlex®NG 5056E, Dow Chemical), characterised by a density of 0.919 g/cm³ and amelt flow index (190° C./2.1 kg) of 1.1, and extruded at a maximumtemperature of 230° C. in a OMC twin-screw extruder. The granules soobtained are blown in a lab-scale Formac blow-extruder at a maximumtemperature of 230° C. to give a film of about 50 μm thickness. UV-Visspectra are recorded in the range 200-800 nm by means of a Perkin-Elmerlambda 20 spectrophotometer, equipped with a RSA-PE-20 Labsphereintegrating sphere. The film displays an absorption in the UV region,with transmittance values below 25% between 300 and 380 nm. Anotherpiece of film of the same composition is stored at room temperatureinside an envelope and between two pieces of paper. The film isperiodically inspected visually to verify possible exudation (blooming)of the compound from the bulk of the polymeric matrix. After 500 hoursno blooming occurred.

EXAMPLE 9

9.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Example 1.1 the oligomer as represented by thestructural formula of above is obtained as a white powder by usingdicyclopentadiene as the monomer and the compound of Example 5.2 as thechain transfer agent.

Visual melting range: 96-108° C.; M_(n): 1400; M_(w): 2400; PDI: 1.71; ε(290 nm, CH₂Cl₂): 4341,

Elemental analysis:

% C % H % O % N theory 85.5 9.6 2.2 2.7 found 83.9 8.9 4.2 3.09.2 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4. They are 150 μm thick and contain 0.5% of the compound.UV-Vis spectra are recorded as described in Example 1.4. The filmdisplays a strong absorption in the range 280-360 nm. Transmittancevalues below 3% are detected in the range 290-350 nm. The persistency ofthe polymer in LOPE films is determined after exposure of the films at60° C. and evaluated as described in Example 1.4. No decrease of theabsorbance value at the maximum is observed after 3000 hours at 60° C.

EXAMPLE 10

1.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Example 9 the oligomer of above is obtained asa yellow powder by using dicyclopentadiene as the monomer and thecompound of Example 8.2.2 as the chain transfer agent.

Visual melting range: 59-64° C.; M_(n): 1320; M_(n): 2220; PDI: 1.68;

Elemental analysis:

% C % H % O % N % Cl theory 80.4 10.1 3.7 3.1 2.7 found 78.3 9.6 6.0 3.22.910.2 Application Example

Thin linear low density polyethylene (LLDPE) films are prepared asdescribed in Example 8.3. They are 50 μm thick and contain 1% of thecompound. UV-Vis spectra are recorded as described in Example 1.4. Thefilm displays an absorption in the UV region, with transmittance valuesbelow 40% between 300 and 380 nm. The compatibility in LLDPE films isdetermined after storage of the films at room temperature and evaluatedas described in Example 8.3. After 300 hours no blooming occurred.

EXAMPLE 11

11.1 Preparation of the Hydrogenated Oligomer of the Formula

To a solution of 92 g (0.050 mol) of the oligomer of Example 11.2 in 300ml of xylene, 1.0 g of platinum on carbon (10% w/w) is added. Themixture is poured into an autoclave and hydrogenated for 24 hours at 65bar (p_(H2)) and 105° C. The hydrogenated mixture is purified from thecatalyst by adding 10 g of Tonsyll© 414 FF at 80-90° C. and left undervigorous stirring for 2 hours. After filtering off over a pad of 10 g ofTonsil the filtrated yellow solution is concentrated under vacuum and apale yellow solid is obtained.

Visual melting range: 55-68° C.; M_(n): 2197; M_(w): 4347; PDI: 1.98; ε(290 nm, toluene): 34574;

Elemental analysis:

% C % H % N theory 85.8 10.2 2.2 found 84.7 10.2 2.011.2 Preparation of the Oligomer of the Formula

30 g (0.056 mol) of the compound from Example 5.2 and 30.2 g (0.320 mol)of norbornylene and 42.3 g (0.320 mol) of dicyclopentadiene and 0.49 g(0.6 mmol) of the catalystbis(tricyclopentylphosphine)dichloro(3-methyl-2-butenylidene)ruthenium(APT Cat ASMC 716) are added to 300 ml of toluene. The mixture is leftto react for 24 hours at 30°. The solution is then concentrated undervacuum and a pale brown solid is obtained.

Visual melting range: 168-180° C.; M_(n): 2216; M_(w): 4663; PDI: 2.10;

Elemental analysis:

% C % H % N theory 87.5 8.4 2.3 found 85.8 8.6 2.111.3 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4. They are 150 μm thick and contain 0.5% of the compound.UV-Vis spectra are recorded as described in Example 1.4. The filmdisplays a strong absorption in the range 280-360 nm. Transmittancevalues below 3% are detected in the range 290-350 nm.

The persistency of the polymer in LDPE films is determined afterexposure of the films at 60° C. and evaluated as described in Example1.4. No decrease of the absorbance value at the maximum is observedafter 3000 hours at 60° C.

EXAMPLE 12

12.1 Preparation of the Hydrogenated Oligomer of the Formula

Following the procedure described in the Example 11.1 the oligomer isobtained as a pale brown product.

M_(n): 962; M_(w): 1599; PDI: 1.66; ε (290 nm, toluene): 8038;

Elemental analysis:

% C % H % N theory 81.2 9.9 2.7 found 80.5 9.9 2.512.2 Preparation of an Oligomer of the Formula

By using as chain transfer agents the compounds from Example 1.3.2 andthe product shown below:

a yellow viscous product is obtained in a manner analogous to Example11.2 M_(n): 981; M_(w): 1680; PDI: 1.71.

12.3 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4. They are 150 μm thick and contain 1.0% of the compound.UV-Vis spectra are recorded as described in Example 1.4. The filmdisplays a strong absorption in the range 280-360 nm. Transmittancevalues below 3% are detected in the range 280-350 nm. The persistency ofthe polymer in LDPE films is determined after exposure of the films at60° C. and evaluated as described in Example 1.4. No decrease of theabsorbance value at the maximum is observed after 1000 hours at 60° C.

EXAMPLE 13

13.1 Preparation of the Hydrogenated Oligomer of the Formula

In a manner analogous to Example 11 and by using the compound of Example12.3 as the chain transfer agent a yellow viscous product is obtained.

M_(n): 1754; M_(w): 3694; PDI: 2.11; ε (290 nm, toluene): 9931;

Elemental analysis:

% C % H % N theory 83.8 11.0 2.4 found 83.3 10.7 3.213.2 Application Example

Thin low density polyethylene (LDPE) films are prepared as described inExample 1.4. They are 150 μm thick and contain 1.5% of the compound.UV-Vis spectra are recorded as described in Example 1.4. The filmdisplays a strong absorption in the range 280-360 nm, with transmittancevalues below 3%. The persistency of the polymer in LDPE films isdetermined after exposure of the films at 60° C. and evaluated asdescribed in Example 1.4. No decrease of the absorbance value at themaximum is observed after 1000 hours at 60° C.

EXAMPLE 14

14.1 Preparation of the Hydrogenated Oligomer of the Formula

According to the method as described in the example 11 and by using thecompound of example 8.2.2 as CTA a yellow viscous product is obtained.

M_(n): 1823; M_(w): 2948; PDI: 1.62; ε (290 nm, toluene): 1778;

Elemental analysis:

% C % H % N % Cl theory 82.3 10.8 2.3 1.9 found 80.3 10.5 3.0 2.514.2 Application Example

Thin linear low density polyethylene (LLDPE) films are prepared asdescribed in Example 8.3. They are 50 μm thick and contain 1% of thecompound. UV-Vis spectra are recorded as described in Example 1.4. Thefilm displays an absorption in the UV region, with transmittance valuesbelow 50% between 300 and 380 nm. The compatibility in LLDPE films isdetermined after storage of the films at room temperature and evaluatedas described in Example 8.3. After 500 hours no blooming occurred.

EXAMPLE 15

15.1 Preparation of the Hydrogenated Oligomer of the Formula

According to the method as described in Example 9 and by using as thechain transfer agent the product reported below:

a pale yellow powder is obtained.

Visual melting range: 127-136° C.; M_(n): 1672; M_(w): 3613; PDI: 2.16;ε (290 nm, toluene): 13290;

Elemental analysis:

% C % H % N theoretic 76.8 9.2 2.5 found 77.0 9.4 2.115.2 Application Example

Thin linear low density polyethylene (LLDPE) films are prepared asdescribed in Example 8.3. They are 50 μm thick and contain 1% of thecompound.

EXAMPLE 16

16.1 Preparation of the Star-shaped Product of Formula

Analogous to the method as described in Example 1.1 and by usingnorbornylene as the monomer and the compound shown below as the chaintransfer agent:

a yellow solid is obtained.

Visual melting range: 85-90° C.; M_(n): 3623; M_(w): 5575; PDI: 1.54; ε(290 nm, toluene): 15643;

Elemental analysis:

% C % H % N theory 79.8 10.5 1.7 found 79.4 10.5 1.616.2 Application Example

Thin linear low density polyethylene (LLDPE) films are prepared asdescribed in Example 8.3. They are 50 μm thick and contain 2% of thecompound. UV-Vis spectra are recorded as described in Example 1.4. Thefilm displays an absorption in the UV region, with transmittance valuesbelow 15% between 300 and 380 nm. The compatibility in LLDPE films isdetermined after storage of the films at room temperature and evaluatedas described in Example 8.3. After 500 hours no blooming occurred.

EXAMPLE 17

17.1 Preparation of the Star-shaped Product of Formula

In a manner analogous to Example 11 and by using the same chain transferagent as in Example 16 a viscous yellow product is obtained.

M_(n): 2549; M_(w): 4352; PDI: 1.71; ε (290 nm,CH₂Cl₂): 27124;

Elemental analysis:

% C % H % N theory 82.6 10.6 2.1 found 81.2 10.5 2.117.2 Application Example

Thin linear low density polyethylene (LLDPE) films are prepared asdescribed in Example 8.3. They are 50 μm thick and contain 1% of thecompound.

EXAMPLE 18

18.1 Preparation of the Star-shaped Product of Formula

In a manner analogous to Example 11 and using as chain transfer agentthe compound reported below:

a yellow resinous product is obtained.

Visual melting range: 59-69° C.; M_(n): 2817; M_(w): 5039; PDI: 1.79; ε(290 nm, toluene): 31089;

Elemental analysis:

% C % H % N theory 83.2 10.6 2.1 found 80.2 10.3 2.118.2 Application Example

Thin linear low density polyethylene (LLDPE) films are prepared asdescribed in Example 8.3. They are 50 μm thick and contain 1% of thecompound.

EXAMPLE 19

19.1 Preparation of the Hydrogenated Oligomers of the Formula

In a manner analogous to Example 1.1 and by using norbornylene as themonomer and as chain transfer agents the compounds from Examples 8.2.2and 5.2 a yellow powder is obtained.

Visual melting range: 111-116° C.; M_(n): 2227; M_(w): 2997; PD): 1.35;ε (290 nm, toluene): 9484;

Elemental analysis:

% C % H % N % Cl theory 83.4 11.1 2.1 1.8 found 83.4 11.1 1.9 1.419.2 Application Example

Thin linear low density polyethylene (LLDPE) films are prepared asdescribed in Example 8.3. They are 50 μm thick and contain 1% of thecompound. UV-Vis spectra are recorded as described in Example 1.4. Thefilm displays an absorption in the UV region, with transmittance valuesbelow 60% between 300 and 380 nm. The compatibility in LLDPE films isdetermined after storage of the films at room temperature and evaluatedas described in Example 8.3. After 500 hours no blooming occurred.

1. A compound of the formula:A—{[_(p)—(X—Y)_(q)][B′_(p′)—(X′—Y′)_(q′)]Z}_(r)  (I), wherein a) one ofq and q′ represents zero, one or a numeral greater than one and theother one represents one or a numeral greater than one; A and Zrepresent chain terminal groups from the chain transfer agent A(—Z)_(r);r represents a numeral from one to four; B and B′ independently of oneanother represent unsaturated or hydrogenated repeating units fromcycloolefins polymerised by metathesis; X and X′ represent identical ordifferent bivalent groups; Y and Y′ represent identical or differentUV-light absorber moieties selected from the group consisting of2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acidesters, oxanilides and 2-(2-hydroxyphenyl)-1,3,5-triazines; and one of pand p′ represents zero, one or a numeral greater than one and the otherone represents one or a numeral greater than one; or wherein b) q and q′represent zero; A and Z represent chain terminal groups from the chaintransfer agent A(—Z)_(r), wherein A represents the chain terminal groupY″—X″—, wherein Y″ represents a UV-light absorber moiety selected fromthe group consisting of 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, benzoic acid esters, oxanilides and2-(2-hydroxyphenyl)-1,3,5-triazines; and X′ represents a bivalent group;and B, B′, p, p′ and r are as defined above.
 2. A compound (I) accordingto claim 1, wherein a) A and Z represent chain terminal groups from amono- (r=1), di- (r=2) or trifunctional (r=3) chain transfer agentA(—Z)_(r); r represents a numeral from one to three; B and B′independently of one another represent an unsaturated or hydrogenatedrepeating unit from cycloolefins polymerised by metathesis selected fromthe group consisting of cyclopropene, cyclobutene, cyclopentene,cycloheptene, cyclooctene, cyclopentadiene, dicyclopentadiene,cyclohexadiene, cycloheptadiene, cyclooctadiene, norbornadiene,norbornene and norbornene derivatives; and X, X′, Y, Y′, p, p′, q and q′are as defined in claim 1; or wherein b) q and q′ represent zero; A andZ represent chain terminal groups from a mono- (r=1), di- (r=2) rtrifunctional (r=3) chain transfer agent A(—Z)r; wherein A representsthe chain terminal group Y″—X″—, wherein Y″ represents a UV-lightabsorber moiety; and X″ represents a bivalent group; and B, B′, p, p′and r are as defined above under a).
 3. A compound (I) according toclaim 1, wherein X, X′ and X″ independently of one another representbivalent groups selected from the group consisting of —O—, —O—C(═O)—,—C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene; and A, B, B′, Y, Y′,Y″, Z, r, p, p′, q and q′ are as defined in claim
 1. 4. A compound (I)according to claim 1, wherein p represents a numeral from 2 to 20; prepresents zero; and A, B, B′, X, X′, X″, Y, Y′, Y″, Z, r, q and q′ areas defined in claim
 1. 5. A compound (I) according to claim 1, whereina) one of q and q′ represents zero, one or a numeral greater than oneand the other one represents a numeral greater than one; A and Zrepresent chain terminal groups from a mono- (r=1), di- (r=2) ortrifunctional (r=3) chain transfer agent A(—Z)_(r); r represents anumeral from one to three; B and B′ independently of one anotherrepresent an unsaturated or hydrogenated repeating unit fromcycloolefins polymerised by metathesis selected from the groupconsisting of cyclopropene, cyclobutene, cyclopentene, cycloheptene,cyclooctene, cyclopentadiene, dicyclopentadiene, cyclohexadiene,cycloheptadiene, cyclooctadiene, norbornadiene, norbornene andnorbornene derivatives; X and X′ independently of one another representbivalent groups selected from the group consisting of —O—, —O—C(═O)—,—C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene; Y and Y′ independentlyof one another represent a UV-light absorber moiety selected from thegroup consisting of 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, benzoic acid esters, oxanilides and2-(2-hydroxyphenyl)-1,3,5-triazines; and p and p′ are as defined inclaim 1; or wherein b) q and q′ represent zero; A represents the chainterminal group Y″—X″—, wherein Y″ represents a UV-light absorber moietyselected from the group consisting of2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acidesters, oxanilides and 2-(2-hydroxyphenyl)-1,3,5-triazines; and X″represents a bivalent group selected from the group consisting of—O—,—O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene; and B,B′, p, p′ and r are as defined above.
 6. A compound (I) according toclaim 1, wherein a) one of q and q′ represents zero or a numeral greaterthan one and the other one represents a numeral greater than one; A andZ represent chain terminal groups from a mono- (r=1), di- (r=2) ortrifunctional (r=3) chain transfer agent A(—Z)_(r); r represents anumeral from one to three; B and B′ independently of one anotherrepresent an unsaturated or hydrogenated repeating unit fromcycloolefins polymerised by metathesis selected from the groupconsisting of cyclopentadiene, dicyclopentadiene, norbornadiene,norbornene and norbornene derivatives; X and X′ independently of oneanother represent bivalent groups selected from the group consisting of—O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene; Y andY′ independently of one another represent a UV-light absorber moietyselected from the group consisting of(2,4-dihydroxyphenyl)-phenylmethanone,2-benzotriazol-2-yl-4-methylphenol, 4-benzotriazol-2-ylbenzene-1,3-diol,3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionicacid, 3-[5-(benzotriazol-2-yl)-3-tert-butyl-4-hydroxyphenyl]-propionicacid, 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene-1,3-diol,4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide; and p and p′ are asdefined in claim 1; or wherein b) q and q′ represent zero; A representsthe chain terminal group Y″—X″—, wherein Y″ represents a UV-lightabsorber moiety selected from the group consisting of(2,4-dihydroxyphenyl)-phenylmethanone,2-benzotriazol-2-yl-4-methylphenol, 4-benzotriazol-2-ylbenzene-1,3-diol,3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionicacid, 3-[5-(benzotriazol-2-yl)-3-tert-butyl-4-hydroxyphenyl]-propionicacid, 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene-1,3-diol,4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide; and X″ represents abivalent group selected from the group consisting of —O—, —O—C(═O)—,—C(═O)—O—, —O(C₁-C₈alkylene)- and C₁-C₈alkylene; and B, B′, p, p′ and rare as defined above.
 7. A compound according to claim 1 of the formula

wherein q represents one; p and p′ together represent a numeral from 2to 20; A represents a chain terminal group from an olefinic chaintransfer agent (CTA); X represents a bivalent group selected from thegroup consisting of —O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)- andC₁-C₈alkylene; and Y represents a UV-light absorber moiety selected fromthe group consisting of 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, benzoic acid esters, oxanilides and2-(2-hydroxyphenyl)-1,3,5-triazines; or wherein q represents zero; p andp′ together represent a numeral from 2 to 20; and A represents the groupY—X—, wherein X represents a bivalent group selected from the groupconsisting of —O—, —O—C(═O)—, —C(═O)—O—, —O(C₁-C₈alkylene)- andC₁-C₈alkylene; and Y represents a UV-light absorber moiety selected fromthe group consisting of 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, benzoic acid esters, oxanilides and2-(2-hydroxyphenyl)-1,3,5-triazines.
 8. A compound according to claim 1of the formula

wherein r represents a numeral from one to three; p and p′ togetherrepresent a numeral from 2 to 20; X represents a bivalent group selectedfrom the group consisting of —O—, —O—C(═O)—, —C(═O)—O—,—O(C₁-C₈alkylene)- and C₁-C₈alkylene; and Y represents a substitutedphenolic group derived from UV-light absorbers selected from the groupconsisting of (2,4-dihydroxyphenyl)-phenylmethanone,2-benzotriazol-2-yl-4methylphenol, 4-benzotriazol-2-ylbenzene-1,3-diol,3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionicacid, 3-[5-(benzotriazol-2-yl)-3-tert-butyl-4-hydroxyphenyl]-propionicacid; 4-(4,6-diphenyl)1,3,5-triazin-2-yl-benzene-1,3-diol,4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin2-yl]-benzene-1,3-diol,4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin2-yl]-benzene-1,3-diol,4-[4,6-bis(4-hydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol andN′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide.
 9. A polymerisatecomprising a metathesis polymer of the formulaA—[B_(p)—(X—Y)_(q)]—A′  (I′) wherein A and A′ represent chain terminalgroups from a chain transfer agent (CTA); B represents an unsaturated orhydrogenated repeating unit from cycloolefins polymerised by metathesis;X represents a bridge group which connects B with the substituent Y; Yrepresents the aromatic substituent of a UV-light absorber selected fromthe group consisting of 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, benzoic acid esters, oxanilides and2-(2-hydroxyphenyl)-1,3,5-triazines; p represents a numeral greater thanone and defines the number of repeating units in the metathesis polymer;and q represents one or a numeral greater than one and defines thenumber of aromatic substituents Y attached with the bridge group X to B.10. A polymerisate according to claim 9 comprising a metathesis polymer(I′), wherein A and A′ represent chain terminal groups from an olefinicchain transfer agent (CTA); B represents an unsaturated or hydrogenatedrepeating unit from cycloolefins polymerised by metathesis selected fromthe group consisting of cyclopropene, cyclobutene, cyclopentene,cycloheptene, cyclooctene, cyclopentadiene, cyclohexadiene,cycloheptadiene, cyclooctadiene, norbornadiene, norbornene andnorbornene derivatives; X represents bivalent atoms or bridge groupsselected from the group consisting of —O—, —O—C(═O)— and —C(═O)—O—; Yrepresents a substituted phenolic group of UV-light absorbers selectedfrom the group consisting of 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, benzoic acid esters, oxanilides and2-(2-hydroxyphenyl)-1,3,5-triazines; p represents a numeral greater thanten; and q represents one or a numeral greater than one.
 11. Apolymerisate according to claim 9 comprising a metathesis polymer (I),wherein A and A′ represent chain terminal groups from an olefinic chaintransfer agent (CTA); B represents an unsaturated or hydrogenatedrepeating unit from cycloolefins polymerised by metathesis selected fromthe group the group consisting of cyclopentadiene, norbornadiene,norbornene and norbornene derivatives; X represents bivalent atoms orbridge groups selected from the group consisting of —O—, —O—C(═O)— and—C(═O)—O—; Y represents a substituted phenolic group of UV-lightabsorbers selected from the group consisting of(2,4-dihydroxyphenyl)-phenylmethanone,2-benzotriazol-2-yl-4-methylphenol, 4-benzotriazol-2-ylbenzene-1,3-diol,3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionicacid, 3-[5-(benzotriazol-2-yl)-3-tert-butyl-4-hydroxyphenyl]-propionicacid, 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene-1,3-diol,4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,N′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide; p represents a numeralgreater than ten; and q represents one or a numeral greater than one.12. A polymerisate according to claim 9 comprising a metathesis polymer(I′), wherein A and A′ represent chain terminal groups from an olefinicchain transfer agent (CTA); B represents a polymer fragment comprisingrepeating units from cycloolefins polymerised by metathesis selectedfrom the group consisting of norbornene-2,5-methoxycarbonyl-norbornene-2, 5-methyl-5-methoxycarbonyl-norbornene-2,5-cyanonorbornene-2, 5-methyl-5-cyanonorbornene,5,5-dicyano-norbornene2,1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-methyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-methyl-6-methoxycarbonyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-methoxycarbonyl-1,4,5,8-dimethano1,4,4a,5,6,7,8,8a-octahydronapthaline,6-cyano-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-ethyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6-ethylidene-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,6,7-dimethyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronapthaline,1,4-dimethano-1,4,4a,9a-tetra-hydrofluorene, dicyclopentadiene,tricyclopentadlene, tetracyclopentadiene, tetracyclododecene and methyltetracyclododecene; X represents bivalent atoms or bridge groupsselected from the group consisting of —O—, —O—C(═O)— and —C(═O)—O—; Yrepresents a substituted phenolic group of UV-light absorbers selectedfrom the group consisting of (2,4-dihydroxyphenyl)-phenylmethanone,2-benzotriazol-2-yl-4methylphenol, 4-benzotriazol-2-ylbenzene-1,3-diol,3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionicacid, 3-[5-(benzotriazol-2-yl)-3-tert-butyl-4-hydroxyphenyl]-propionicacid; 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene1,3-diol,4-[4,6-bis(biphenyl-4-yl]-1,3,5-triazin-2-yl]-benzene-1,3-diol,4-[4,6-di-(2,4-dihydroxyphenyl)-1,3,5-triazin-2-yl]-benzene-1,3-diol andN′-2-ethylphenyl-N′-2-hydroxyphenyloxalamide; p represents a numeralgreater than ten; and q represents one or a numeral greater than one.13. A polymerisate according to claim 9 comprising a metathesis polymerhaving the formula

wherein A and A′ represent chain terminal groups from an olefinic chaintransfer agent (CTA); X represents a bridge group which connects A′ withY; Y represents a substituted phenolic group of UV-light absorbersselected from the group consisting of2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acidesters, oxanilides and 2-(2-hydroxyphenyl)-1,3,5-triazines; r representszero or one; and n and n′ represent numerals greater than zero.
 14. Apolymerisable composition comprising a) a catalytically effective amountof a penta- or hexavalent ruthenium or osmium carbene catalyst capableof performing ring opening metathesis polymerisation of cycloolefins;and b) the chain transfer agent A(—Z)_(r) and monomers capable offorming a compound of the formulaA—{[B_(p)(X—Y)_(q)][B′_(p)—(X′—Y′)_(q′)]Z}_(r)  (I), wherein A, B, B′,X,X′, Y, Y′, Z, r, p, p′, q and q′ are as defined in claim
 1. 15. Apolymerisable composition according to claim 14 comprising a) acatalytically effective amount of a penta- or hexavalent ruthenium orosmium carbene catalyst of the formulae:

wherein Me represents ruthenium; L_(a) and L_(b) independently of oneanother represent anionic ligands; L¹, L² and L³ independently of oneanother represent monodentate, neutral e⁻ donor ligands; and Rrepresents aryl, arylthio or C₃-C₅-alkenyl; and b) the chain transferagent A(—Z)_(r) and monomers capable of forming the compound (I)according to claim 4, wherein A, B, B′ X, X′, Y, Y′, Z, r, p, p′, q andq′ are as defined in claim
 14. 16. A polymerizable composition accordingto claim 14, wherein the catalytically effective amount of a penta- orhexavalent ruthenium carbene catalyst is selected from the groupconsisting of

wherein iPr represents isopropyl, Cy represents cyclohexyl and Cypentrepresents cyclopentyl.
 17. A composition comprising α) a composition ofmatter susceptible to degradation induced by light, heat or oxidation;and β) the compound (I) according to claim 1, wherein A, B, B′ X, X′, Y,Y′, Z, r, p, p′, q and q′ are as defined in claim
 1. 18. A compositionaccording to claim 17, wherein the composition of matter susceptible todegradation induced by light, heat or oxidation is selected from thegroup consisting of LDPE, LLDPE, EVA, PP and PET.
 19. A method forstabilizing a composition of matter against degradation induced bylight, heat or oxidation, which comprises incorporating within thecomposition of matter a degradation effective amount of a compound (I)according to claim 1, wherein A, B, B′ X, X′, Y, Y′, Z, r, p, p′, q andq′ are as defined in claim
 1. 20. A method according to claim 19 forselectively screening the light radiation to which plants are exposedwithin green houses, which comprises incorporating within a green housefilm material an effective amount of a compound (I) according to claim19.
 21. A method according to claim 19 for selectively screening thelight radiation to which packed food is exposed, which comprisesincorporating within a covering film material an effective amount of acompound (I) according to claim 19.